U.S. Pat. No. 8,178,658 discloses pesticidal compositions comprising a compound having the following structure:
wherein Ar1, Het, Ar2, J, L, K, Q, R1, R2, R3, and R4 are disclosed in the patent. While processes are disclosed on how to make such compounds, and such processes are useful, it is desired to have more useful processes to make these compounds. In particular, it is desirable to have more commercially useful routes to certain substituted triaryl intermediates disclosed in the patent that are useful in producing the compounds of Formula A-1.Description of the Disclosure
Throughout this document, all temperatures are given in degrees Celsius, and all percentages are weight percentages unless otherwise stated.

Haloalkoxyarylhydrazines of Formula 1.2, wherein R is a (C1-C6)haloalkoxy, such as, but not limited to, trifluoromethoxy and pentafluoroethoxy, can be prepared as illustrated in Scheme 1. In general, in step a, a haloalkoxyaniline of Formula 1 is reacted with sodium nitrite (NaNO2) to produce an intermediate diazonium salt of Formula 1.1. In step b, the intermediate diazonium salt is reduced to form haloalkoxyarylhydrazines of Formula 1.2.
In Step a, approximately a 1:1 molar ratio of the haloalkoxyaniline and NaNO2 may be used, however, molar ratios of about 1:2 may also be used. This reaction is conducted in a polar, protic solvent. Suitable examples of polar, protic solvents are water, formic acid, n-butanol, isopropanol, ethanol (EtOH), methanol (MeOH), acetic acid (AcOH), or mixtures thereof. Currently, it is preferred if water is used. Furthermore, Step a is conducted in the presence of an inorganic acid. Suitable examples are hydrochloric acid (HCl), nitric acid (HNO3), phosphoric acid (H3PO4), sulphuric acid (H2SO4), boric acid (H3BO3), hydrofluoric acid (HF), hydrobromic acid (HBr), perchloric acid (HClO4), tetrafluoroboric acid (HBF4), or mixtures thereof. Currently, it is preferred if HCl is used. The pH of the reaction is from about −1 to about 4, preferably from about −1 to about 1. The reaction is conducted at a temperature from about −10° C. to about 5° C. and preferably from about −5° C. to about 5° C. The reaction is conducted at about atmospheric pressure, however, higher or lower pressures can be used.
Step b is conducted in a polar, protic solvent. Suitable examples of polar, protic solvents are water, formic acid, n-butanol, isopropanol, nitromethane, EtOH, MeOH, AcOH, or mixtures thereof. Currently, it is preferred if water is used. This reaction is conducted in the presence of a reducing agent, such as, for example, sodium dithionite (Na2S2O4), tin (II) chloride (SnCl2), hydrogen, and ammonium formate. The pH of the reduction reaction mixture is from about 8 to about 14, and preferably from about 9 to about 12. The reaction is conducted at a temperature from about −10° C. to about 10° C. preferably about −5° C. to about 5° C. The reaction is conducted at about atmospheric pressure, however, higher or lower pressures can be used.
If desired, the haloalkoxyarylhydrazines can be obtained as a salt or a free base ((HX)n where n=0, 1, or 2) with pH adjustments following the reaction in step b.
A particularly preferred haloalkoxyarylhydrazine of Formula 1.2. is
